Method of making a dithiophosphoric acid of an alkyl-substituted phenol and a mineral oil containing this compound



Patented Oct. 9, 1945 UNITED STATES PATENT OFFICE Orland M. Reiff andHarry J. Andreas, Jr., Woodbury, N. .L, assignors to Socony-Vacuum OilCompany, Incorporated, a corporation of New York AN ALKYL-SUBSTI- NoDrawing. Application May 29, 1943, Serial No. 489,086

12 Claims.

This invention has to do with a method of making dithiophosphoric acidsof alkyl-substituted hydroxyaromatic compounds, and particularly has todo with a method of making the dithiophosphoric acids of wax-substitutedhydroiwaromatic compounds.

In the prior art, such as that disclosed in a copending application,Serial No. 390,586, died April 26, 1941, in which one of the presentinventors, O. M. Reid, is a co-inventor, the prevailing method for thepreparation of dithiophosphoric acids of alkyl-substitutedhydroxyaromatic compounds is shown to be one involving a reaction of analkyl-substituted hydroxyaromatic compound with P285 under suitablereaction conditions. In the method under discussion, an alkylsubstitutedhydroxyaromatic compound is formed in a Friedel-Cratts reaction of analkyl halide and a hydroxyaromatic compound and isolated from theFriedel-Crai'ts catalyst used therein, and is then reacted with P285 toform a dithiophosphoric acid of the alkyl-substituted hydroigvaromaticcompound. While the yields of dithiophosphoric acids of this type arerelatively good with this method, the acids are comparatively impure andtend to decompose, with the evolution of Hfi, when heated. They arerather undesirable for certain uses because of their odor and darkcolor.

The present invention is predicated upon the discovery of a new methodfor making improved dithiophosphoric acids of the aforesaid type ingreater yields. The acids obtained in the new method are superior tothose obtained as described hereinabove in that they are lighter incolor, are less odorous, are more stable to heat, etc. Not only are theacids so improved, but the metal salts of said acids are characterizedas well by a similar improvement over the corresponding metal salts ofthe acids obtained by the method already described. Accordingly, thepresent method is contemplated as a superior means for preparing metalsalts, and other derivatives, of dithiophosphorlc acids ofalkyl-substituted hydroxyaromatic compounds as well as for preparingsaid acids.

The method contemplated herein involves reacting an alkyl halide with ahydroxyaromatic compound in the presence of a Friedel-Crafts catalyst,then reacting the Friedel-Crafts reaction mixture with P285. and finallyremoving the Friedel-Crafts catalyst and isolating the desireddithiophosphoric acid.

While the preceding statement is a concise description of the newmethod, the method will tailed discussion. Initially, an alkyl halideand a hydroxyaromatic compound are reacted in the presence of a small orcatalytic amount of a Friedel-Crafts catalyst, such for example asA1011. A particularly desirable manner for effecting this reaction isthat of first admixing the halide and ,hydroxyaromatic compound, thenadding AlCla be more fully understood from the following deat a rateslow enough to avoid excessive foaming caused by the evolution oihydrogen chloride. After the complete addition of AlCh, the reactiontemperature is raised to complete the reaction. The reaction product atthis stage is the aluminum aryl oxide of the alkyl-substttutedhydroxyaromatic compound.

Then, P285 is added to the reaction product and the resulting mixtureheated at a temperature of about 175 C. until hydrogen sulfide is nolonger evolved. A substantially inert diluent, such as a minerallubricating oil fraction may be used in the reaction with P285; such a,diluent is required, however, for mixtures of high viscosity such asthat oi the illustrative example shown hereinafter.

The P285 reaction mixture obtained above is then cooled, as to about C.,and water added, with stirring, in order to decompose the MCI: complex.Water washing is continued until a water extract free of A101: isobtained. Any emulsions that may be formed in the water washingoperation may be broken by adding small amounts of suitable polarmaterials, such as alcohols, typical of which are butanol and fusel oil.The reaction product, separated from the water washings, is thenfiltered through a. suitable illter medium such as a diatomaceous earth,Hi-Flo, a chemically calcined natural, diatomaceous silica aid of thefinest pore size. The filtrate so obtained is then distilled to removeany diluent used in the P285 reaction, and to remove any polarmaterials, as butanol, used in breaking emulsions formed in thewater-washing treatment. It is desirable at this point to introducesteam at a temperature of about 300" F. to insure complete removal oflight solvents. Steaming is ordinarily continued until an amount ofwater distillat equal in volume to the product is obtained. The portionnot distilling in the distillation step will be the final product, adithiophosphoric acid of an alkyl-substituted hydroxyaromatic compound.

It has also been found that further improvement in color and stabilitycan be obtained by adding a small amount, such as about 1%, of zinc dustto the P285 reaction mixture durin the treatment with water at atemperature of about 100 0., as described above. In this recard, it hasbeen noted that a small amount of zinc dust may also be so utilized as amodification of the old method referred to hereinabove, and when soutilised cooperates to produce a product of improved color andstability, although such products are not as desirable in these respectsas are those obtained by carrying out the Pass reaction in the presenceof the Friedei- Crafts reaction mixture, nor are they as desirable asthose obtained by the latter method when a small amount of line dust isused therein. In the old method, a wax-phenol and Past are reacted atabout 175 C. for some time, then cooled to about 90-100 0. As newdiscovered, improved products can be obtained by adding, at this point,a small amount of zinc dust together with a small amount of water andthen stirring the resulting mixture. Water is removed thereafter byheating said mixture at about 110 C., and the water-free mixture isfiltered through a suitable fllter medium to obtain the final product.

Metal salts of the dithiophosphoric acid so obtained can be prepared byany one of several ways, such as those ducribed in the aforesaidcopending application, Serial No. 390,586. For example, the sodium saltmay be prepared by reacting said acid with a sodium alcoholate, and thendistilling oi! the alcohol. Other metal salts can be prepared from thesodium salt by metathesis with a suitable metal compound such as ahalide. And as indicated above, when a substantially inert diluent isused in the reaction of P235 with the alkyl-substituted hydronaromaticcompound, the diluent may be removed prior to the formation of a metalsalt or may be removed after the metal salt has been formed. Also amineral lubricating oil concentrate or blend containing a metal salt ofthe foregoing type may be prepared by using a mineral lubricating oil asthe diluent.

With regard to the proportions of reactants used in the foregoing, itwill be obvious that the amount of alkyl halide and hydroxyaromaticcompound can be varied considerably depending upon the desired degree ofalkyl substitution. The amount of Past can also vary widely; however, itis preferred that this amount represent about 1 to 2 mols for every 4mols of alkyl-substituted hydroxyaromatic compound formed in theFriedei-Crafts reaction. The reaction wherein 8. mol ratio of 1 to 4 isused may be represented by the following Equation 1:

s 1 4s-'r on+r,s. 2(R-TO):-SH+H:S

wherein R represenin an alkyl group and '1' represents an aromaticnucleus.

The formation of the metal salts of the dithiophosphoric acids describedin Equation I may be represented by the following Equation II in which ametal hydroxide is used:

wherein R and T are as defined above and M represents the hydrogenequivalent of a metal.

The reaction product obtained by using a mo] ratio of 2 to 4 is morecomplex than that represented by the foregoing Equation I and is amixture of a dithlophosphoric acid derivative and other constituents.

It will be apparent from the foregoing that the newly discovered methoddiiiers from that of alyst is present during the reaction with P285, andis removed prior to the introduction of P285 in the old method. Forexample, in the present method, when phenol is reacted with chlorowax inthe presence of aluminum chloride, a wax aluminum phenate is formed asan intermediate product which is then reacted with P285 to form thealuminum salt of the dithiophosphoric acid of a wax phenol; the aluminumsalt is then washed with water to decompose the salt and liberate thefree dithiophosphoric acid. On the other hand, when the same reactantsand catalyst were used in prior practice, wax aluminum phenate wasformed; it was then washed with water to decompose the salt and liberatea free wax phenol: the wax phenol was separated from the Friedel-Craftscatalyst, which is at this sta generally in the form of a complex, andfinally reacted with P285 to form the dithiophosphoric acid of a waxphenol.

Examples of the hydroxyaromatic compounds which may be used as startingmaterial for the Frledel-Crafts reaction with an alkyl halide. such aschlorowax are: phenol, resorcinol, hydroquinone, catechol, cresol,xylenol, hydroxydiphenyl, benzylphenol, phenyl-ethyl-phenol, phenolresins, methyl-hydroxy-dlphenyl, guiacol, alphaand beta-naphthol,alphaand beta-methyl naphthol, tolyl naphthol, xylyl naphthol, benzylnaphthol, anthranol, phenyl methyl naphthol, phenanthrol, monomethylether of catechol, anisole beta naphthyl methyl ether, chlorphenol, andthe like. Preference in general is to the monohydroxy phenols otherwiseunsubstituted, particular preference being given to phenol and alphaandbeta-naphthol.

In general, all alkyl halides such as the chicrides of the relativelylow molecular weight parafllns typified by methyl, ethyl, propylchlorides, etc., and the heavy alkyl chlorides can be used in the methodcontemplated herein. The halides, and particularly the chlorides, of therelatively high molecular weight paraiilns are desirable for use inpreparing dithiophosphoric acids, and their corresponding metal salts,which are characterized by substantial miscibility or solubility inhydrocarbon fractions, such as mineral lubricating oils. Representativeof the relatively high molecular weight halides, and preferred for useherein, are those known in the art as wax halides obtained by thehalogenation of wax. For example, petroleum wax which is a paramnichydrocarbon obtained from petroleum and has at least eighteen carbonatoms in the molecule, can be chlorinated to various degrees to obtainseveral chlorine-substituted waxes, such as monochlorowax, dichlorowax,etc. Particular preference is given to chlorowaxes obtained bychlorination of a petroleum wax having a melting point not substantiallyless than 120 F., a molecular weight of about 250 and about 20 carbonatoms to the molecule. It will be understood from this description thatthe term chlorowax" when used herein will refer to a material containingone or more chlorine atoms and a relatively high molecular weight alkylgroup or radical obtained from a hydrocarbon fraction identified as wax.

For example, wax-substituted phenol prepared according to the aboveprocedure, in which a quantity of chlorowax containing three atomicproportions of chlorine is reacted with one mol of phenol and in whichthe chlorowax contains twenty per cent chlorine, will for brevity hereinbe designated "wax-phenol (3-20)." Parenthetthe prior art inasmuch asthe Friedel-Crafts catical expressions of the type (A-B) may be usedaseacov hereinafter in connection with the alkylhydroxyaromaticcompounds to designate: (A) the number of atomic proportions of chlorinein the chloraliphatic material reacted with one moi of hydroxyaromaticcompound in the Friedel-Crai'ts reaction and (B) the chlorine content ofthe chloraiiphatic material. In the above example, 11:3 and 8:20. Thissame designation will also apply to the dithiophosphoric acids, andtheir metal salts, of these alkylated compounds.

Although any of the catalysts of the group known as Friedel-Craftscatalysts can be used in the present method, it is preferred thataluminum chloride be used.

The metals contemplated herein may be broad- 1y classified as metals ofgroups I to VIII, inclusive, of the periodic system, which are capableof forming salts of the aforesaid dithiophosphoric acids. These metalscomprise the following: the alkali metals: lithium, sodium, potassium,rubidium and caesium; the alkaline earth metals: beryllium, magnesium,calcium, strontium and barium; the metals zinc, cadmium, mercury,scandium; the metals aluminum, gallium, indium, thallium, titanium,zirconium, cerium, thorium; germanium, tin, and lead; vanadium,columbium and tantalum; arsenic, antimony an bismuth: chromium,molybednum, tungsten and uranium; rhenium, manganese, iron, cobalt andnickel; ruthenium, rhodium and palladium; osmium, iridium and platinum.

Some of the rare earth metals are given in the foregoing. Other rareearth metals suitable for the formation of the dithiophosphoric acidsalts are those now commercially available as the cerium and yttriumgroup: namely, a mixture of praseodymium, neodymium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thallium and lutecium.

Farther details in the new method of preparation contemplated hereinwill be apparent from the following illustrative example.

Examm 1 Preparation of Dithiophosphoric acid of war phenol (3-14)Petroleum wax of A, S. T. M, melting point of 126 F. (about 52 C.) waschlorinated by introducing chlorine at about 100 C. until 14 per cent byweight of chlorine was adsorbed. One hundred grams of the chlorowax soobtained were mixed with 12.3 grams of phenol, and 3 grams of A101: wereadded at about 65 C. at a rate slow enough to avoid excessive foamingcaused by the evolution of hydrogen chloride. The reaction temperaturewas then raised to 1'15 C. and the mixture was stirred for about onehour at this temperature to complete the reaction. The product at thisstage was the aluminum phenate of wax phenol (3-14).

A solvent refined mineral oil (207 grams) of Saybolt Universal viscosityof 45 seconds at 210 F. was then added, followed by 1.4 grams of Past.The resulting mixture was then heated for four hours longer at 175 C.The reaction with P285 was largely completed after one hour at thistemperature as indicated by the decrease in the amount of H28 evolved;however, the reaction mixture was heated longer to insure completion ofthe reaction. The reaction mixture was then cooled to about 100 C. andwater was carefully added with stirring to decompose the aluminumchloride complex. The color of the reaction mixture was lightened atthis point by the addition of 5 grams of zinc dust. Several washingswith ,said corresponding compounds.

water were required to obtain a water extract free of aluminum chloride.Small amounts of butanol were added to break emulsions formed on theaddition of water. The product was filtered through Hi-Flo, and thebutanol distilled from the flitrate by using reduced pressure, followedby steaming at about C. until an amount of water distillate equal to thevolume of the product was obtained. The product obtained was a 1:3 blendin mineral oil, which contained 0.6 per cent phosphoru and 1.0 per centsulfur, and had a neutralization number (N. N.) of 6.3. These valuesapproximate the theoretical values for the dithiophosphorie acid ofwax-phenol (3-14).

In view of the foregoing discussion, it will be clear to those familiarwith the art that a dithiophosphoric acid of the foregoing type will beobtained free from oil when a diluent is not used in the preparation, orwhen a lower boiling diluent such as kerosene, which can be removedthereafter by distillation, is used. It will be apparent, then, that thepresent method provides a particularly desirable means for preparingdithiophosphoric acids (and their metal salts) of alkyl-substitutedhydroxyaromatic compounds per se and in the form of mineral oilconcentrates.

That the compounds obtained by the present method are more stable toheat than the corresponding compounds obtained by previous methods isclearly shown by their behavior under normal storage conditions. Thosecompounds obtained by previous methods continue to evolve hydrogensulfide slowly under such conditions, which is indicative of theirrelative instability. On the other hand, the corresponding compoundsobtained by the present method are not so characterized, for they can beheated to about lilo-200 C. before hydrogen sulfide is first evolved.

The compounds obtained in this method are valuable as multifunctionalmineral oil addition agent inasmuch as they effect substantialimprovement of such properties as pour point, viscosity index, oxidationcharacteristics, etc, when used in small amounts in mineral oils. Theyare particularly desirable for use in oils as they impart less color tothe oils in which they are incorporated, than do the correspondingcompounds prepared by previous methods, discussed above. Also, they aredesirable in this regard for they are less odorous and more stable toheat than For example, a one per cent blend of a barium salt of areaction product of wax-phenol and P285, obtained by the methodcontemplated herein, in a mineral oil fraction had a Tag Robinson colorof 11; whereas, a similar one per cent blend, the corresponding bariumsalt prepared by the old method described hereinabove had a Tag Robinsoncolor of only 2 The color values of the corresponding free acidderivatives of these barium salts were approximately the same as thevalues for said salts.

Similarly, the compounds obtained by the improved method wherein a smallamount of zinc dust is used without carrying out the Pass reaction inthe presence of the Friedel-Crafts complex, are superior to thoseobtained by the old method referred to hereinabove. As an illustration,a one per cent blend of the barium salt of a reaction product ofwax-phenol and P285, obtained by the old method modified by the use ofsaid zinc dust, in a mineral oil fraction had a Tag Robinson color of 5as against a. color oi 2% for the corresponding blend of the relatedcompound obtained by the old method.

We claim:

1. The method of making a dithiophosphoric acid of an alkyd-substitutedphenol which comprises: reacting an alkyl halide with a phenol in thepresence of a Friedel-Crafts catalyst to alkylate said phenol; thenreacting the reaction mixture, formed in the first operation, with P255to form a dithiophosphoric acid of an alkyl-substituted phenol; andseparating said dithiophosphoric acid from the reaction mixture formedin the last-mentioned operation.

2. The method of making a. dithiophosphoric acid of an alkyl-substitutedphenol which comprises: reacting an alkyl halide with a phenol in thepresence of a Friedel-Craits catalyst to alkyiate said phenol; thenreacting the reaction mixture, formed in the first operation, with P235to form a dithiophosphoric acid of an alkyl-substituted phenol, themolal quantity of P235 so reacted being about one-fourth as much as thealkyl-substituted phenol in said reaction mixture; treating the Passreaction mixture thus obtained with a small amount of zinc dust andwashing the reaction mixture so formed with water to destroy theFriedel-Crafts complex formed in the preceding operations, andseparating said dithiophosphoric acid therefrom.

3. The method of making a dithiophosphoric acid of a paraiiln wax-phenolwhich comprises: reacting a chlorinated paraiiin wax and phenol in thepresence of a catalytic amount of A161: at a temperature not greaterthan about 175 C. to alkylate phenol with parailin wax; then reactingthe reaction mixture, formed in the first operation, with P255 in thepresence of a substantiallyinert hydrocarbon diluent to form adithiophosphoric acid of a parafl'ln wax-phenol, the molal quantity ofPass so reacted being about one-fourth as much as the paraflinwax-phenol in said reaction mixture; washing the reaction mixture,formed in the preceding operation, with water to destroy theFriedel-Craits complex formed in the preceding operations, andseparating said dithiophosphoric acid therefrom.

4. The method of making a dithiophosphoric acid of a paraflln wax-phenolwhich comprises: reacting a chlorinated paraffin wax and phenol in thepresence of a catalytic amount of AlCls at a temperature not greaterthan about 175 C. to alkylate phenol with parailin wax; then reactingthe reaction mixture, formed in the first operation, with P285 in thepresence of a substantially-inert hydrocarbon diluent to form a.dithiophosphoric acid of a para-fli wax-phenol, the racial quantity ofP285 so reacted being about one-fourth as mpch as the parafllnwax-phenol in said reaction mixture; treating the P285 reaction mixturethus obtained with a small amount of zinc dust at about 100 C. andwashing the reaction mixture so formed with water to destroy theFriedel-Crafts complex formed in the preceding operations, andseparating said dithiophosphoric acid therefrom.

5. The method of making a metal salt of a dithiophosphoric acid of analkyl-substituted phenol which comprises reacting an alkyl halide with aphenol in the presence of a Friedal-Craits catalyst to alkylate saidphenol; then reacting the reaction mixture, formed in the firstoperation, with P285 in the presence of a substantiallyinert hydrocarbondiluent to form a dithiophosphoric acid of an alkyl-substituted phenol,the

molal quantity of Passsoreactedbeingablmt oneiourth as much as the alkylsubstituted phenol in said reaction mixture; washing the reocflonmixture, formed in the preceding operltlm, with water to destroy thePriedel-Crai'h cunplex formed in the preceding operations, andseparating said dithiophosphoric acid theretnnn; and substituting saiddithiophosphoric acid with metal.

6. The method oi making a metal salt of a dithiophosphoric acid of aparaflln Iax-mbsfltuted phenol which comprises: reacting a chlorinatedparaihn wax with a phenol in the presence of a Friedel-Crafts catalystto aibiate said phenol with paraiiln wax: then reacting the reactionmixture, formed in the first operaflm, with P286 in the presence of asubstantially-inert hydrocarbon diluent to form a dithiophosphonc acidof a paraflin wax-substituted phenol, the moial quantity of P285 soreacted being about onefourth as much as the parailin wax-substitutedphenol in said reaction mixture; the reaction mixture, formed in thepreceding operation, with water to destroy the Ffledei-Craits complexformed in the preceding perations, and separating said dithiophosphoricacid therefrom; and substituting said dithiophosphoric acid with metal.

7. The method of making a mineral 01! concentrate containing adithiophosphoric acid of an aikyl-substituted phenol which comprise:reacting an alkyl halide and a. phenol in the presence of aFriedel-Cratts catalyst to alkylate said phenol; then reacting thereaction mixture. formed in the first operation, with Pfic in thepresence of a substantially-inert mineral oil to form a mineral oilconcentrate containing a dithiophosphoric acid of an dbl-substitutedphenol, the amount of P235 so reacted being about one-fourth as much asthe alkyi-suhstituted phenol in said reaction mixture; washing thereaction mixture, formed in the preceding operation, with water todestroy the Friedel-Crafts complex formed in the preceding operations;and separating said mineral oil concentrate from the reaction mixtureformed in the preceding operation.

8. The method of making a mineral oil concentrate containing adithiophosphoric acid of a parafiin wax-substituted phenol. whichcomprises: reacting a chlorinated paraffin wax and a phenol in thepresence of a FriedeiCraits catalyst to alkylate said phenol withparailln wax; then reacting the reaction mixture, formed in the firstoperation, with PzSs in the presence of a substantially-inert mineraloil to form a mineral oil concentrate containing adithiophosphoric acidof a parafiin wax-substituted phenol, the amount of P255 so reactedbeing about one-fourth as much as the parailin wax-substituted phenol insaid reaction mixture; washing the reaction mixture, formed in thepreceding operation, with water to destroy the Friedel-Crafts complexformed in the preceding operations; and separating said mineral oilconcentrate from the reaction mixture formed in the preceding operation.

9. The method of making a mineral oil concentrate containing a metalsalt of a dithiophosphoric acid oi an alkyl-substihited phenol, whichcomprises: reacting an alkyl halide and a phenol in the presence of amodel-Crafts catalyst to alkylate said phenol; reacting the reactionmixture, formed in the first operation, with P285 in the presence of asubstantially-inert mineral oil to form a mineral oil concentratecontaining a dithiophosphoric acid of an alkyl-substituted phenol, theamount of P285 so reacted being about one-fourth as much as thealkyl-substituted phenol in said reaction mixture; washing the reactionmixture, formed in the preceding operation, with water to destroy theFriedel-Crafts complex formed in the preceding operations, andseparating said mineral oil concentrate containing said dithiophosphorieacid therefrom; and substituting said dithiophosphoric acid with metalto form a mineral oil concentrate containing a metal salt of saiddithiophosphoric acid.

10. The method of making a mineral all concentrate containing a metalsalt of a dithiophosphoric acid of a paraflin wax-substituted phenol,which comprises: reacting a chlorinated paramn wax and a phenol in thepresence of a Friedel- Crafts catalyst to alkylate said phenol withparaffln wax; reacting the reaction mixture, formed in the firstoperation, with Pass in the presence of a substantially-inert mineraloil to form a mineral oil concentrate containing a dithiophosphoric acidof a paraflln wax-substituted phenol, the amount of P185 so reactedbeing about one-fourth as much as the paraflin wax-substituted phenol insaid reaction mixture; washing the reaction mixture formed in thepreceding operation with water to destroy the Friedel-Oraits complexformed in the preceding operations, and separating said mineral oilconcentrate containing said dithiophosphorlc acid therefrom; andsubstituting said dithiophosphoric acid with metal to form a mineral oilconcentrate containing a metal salt 01' said dlthiophowhoric acid.

11. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion of edithiophosphoric acid 01' an align-substituted phenol obtained by:reacting an alkyl halide with a phenol in the presence or aFriedel-Crafts catalyst to alkylate said phenol; then reacting thereaction mixture, formed in the first operation, with P285 to form adithiophosphoric acid of an alkyl-substituted phenol, the molal quantityof P285 so reacted being about one-fourth as much as thealkyl-substituted phenol in said reaction mixture; washing the reactionmixture, formed in the preceding operation, with water to destroy theFriedel-Crafts complex formed in the preceding operations; andseparating said dithiophosphoric acid from the reaction mixture formedin the last-mentioned operation.

12. An improved mineral oil position comprising a viscous mineral oilfree on having in admixture therewith a minor proportion of a metal saltor a dithiophosphoric acid of an allwisubstituted phenol obtained by:reacting an alkyl halide with a phenol in the presence of aFriedel-Craits catalyst to alkylate said phenol; then reacting thereaction mixture, formed in the first operation, with P255 to form adithiophosphoric acid of an aikyl-substituted phenol, the molai quantityof Pass so reacted being about one-fourth as much as the chm-substitutedphenol in said reaction mixture; washing the reaction mixture, formed inthe preceding operation, with water to destroy the Frledel-Crattscomplex formed in the preceding operations; separating saiddithiophosphoric acid from the reaction mixture formed in thelast-mentioned operation; and substituting said dlthiophosphoric acidwith metal.

ORLAND M. REIF'F. HARRY J, ANDRESS, Jn.

GBR'I'IFICA'JZE OF CORREC'HON.

Patent no, 2,386,207.

Ootober 9, 1915.

ORIANID H. REIPF, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,second column, 11110 37, before "aid" insert the word "filter";

said Letters Patent should be read with this correction therein that thesome may conform to the record of the case in the Patent Office.

Signed and 801166. this 9m do! or April, A. 1:. 19%.

(Seal) Leslie Frazer First Assistant Commissioner of Patents.

ans that the a dithiophosphoric acid of an alkyl-substituted phenol, theamount of P285 so reacted being about one-fourth as much as thealkyl-substituted phenol in said reaction mixture; washing the reactionmixture, formed in the preceding operation, with water to destroy theFriedel-Crafts complex formed in the preceding operations, andseparating said mineral oil concentrate containing said dithiophosphorieacid therefrom; and substituting said dithiophosphoric acid with metalto form a mineral oil concentrate containing a metal salt of saiddithiophosphoric acid.

10. The method of making a mineral all concentrate containing a metalsalt of a dithiophosphoric acid of a paraflin wax-substituted phenol,which comprises: reacting a chlorinated paramn wax and a phenol in thepresence of a Friedel- Crafts catalyst to alkylate said phenol withparaffln wax; reacting the reaction mixture, formed in the firstoperation, with Pass in the presence of a substantially-inert mineraloil to form a mineral oil concentrate containing a dithiophosphoric acidof a paraflln wax-substituted phenol, the amount of P185 so reactedbeing about one-fourth as much as the paraflin wax-substituted phenol insaid reaction mixture; washing the reaction mixture formed in thepreceding operation with water to destroy the Friedel-Oraits complexformed in the preceding operations, and separating said mineral oilconcentrate containing said dithiophosphorlc acid therefrom; andsubstituting said dithiophosphoric acid with metal to form a mineral oilconcentrate containing a metal salt 01' said dlthiophowhoric acid.

11. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion of edithiophosphoric acid 01' an align-substituted phenol obtained by:reacting an alkyl halide with a phenol in the presence or aFriedel-Crafts catalyst to alkylate said phenol; then reacting thereaction mixture, formed in the first operation, with P285 to form adithiophosphoric acid of an alkyl-substituted phenol, the molal quantityof P285 so reacted being about one-fourth as much as thealkyl-substituted phenol in said reaction mixture; washing the reactionmixture, formed in the preceding operation, with water to destroy theFriedel-Crafts complex formed in the preceding operations; andseparating said dithiophosphoric acid from the reaction mixture formedin the last-mentioned operation.

12. An improved mineral oil position comprising a viscous mineral oilfree on having in admixture therewith a minor proportion of a metal saltor a dithiophosphoric acid of an allwisubstituted phenol obtained by:reacting an alkyl halide with a phenol in the presence of aFriedel-Craits catalyst to alkylate said phenol; then reacting thereaction mixture, formed in the first operation, with P255 to form adithiophosphoric acid of an aikyl-substituted phenol, the molai quantityof Pass so reacted being about one-fourth as much as the chm-substitutedphenol in said reaction mixture; washing the reaction mixture, formed inthe preceding operation, with water to destroy the Frledel-Crattscomplex formed in the preceding operations; separating saiddithiophosphoric acid from the reaction mixture formed in thelast-mentioned operation; and substituting said dlthiophosphoric acidwith metal.

ORLAND M. REIF'F. HARRY J, ANDRESS, Jn.

GBR'I'IFICA'JZE OF CORREC'HON.

Patent no, 2,386,207.

Ootober 9, 1915.

ORIANID H. REIPF, ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,second column, 11110 37, before "aid" insert the word "filter";

said Letters Patent should be read with this correction therein that thesome may conform to the record of the case in the Patent Office.

Signed and 801166. this 9m do! or April, A. 1:. 19%.

(Seal) Leslie Frazer First Assistant Commissioner of Patents.

ans that the

